US8167600B2 - Apparatus for producing polymer film and process for producing polymer film - Google Patents
Apparatus for producing polymer film and process for producing polymer film Download PDFInfo
- Publication number
- US8167600B2 US8167600B2 US11/912,970 US91297006A US8167600B2 US 8167600 B2 US8167600 B2 US 8167600B2 US 91297006 A US91297006 A US 91297006A US 8167600 B2 US8167600 B2 US 8167600B2
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- 238000000034 method Methods 0.000 title abstract description 14
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- 238000012545 processing Methods 0.000 claims description 52
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- 238000001035 drying Methods 0.000 abstract description 23
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H20/00—Advancing webs
- B65H20/20—Advancing webs by web-penetrating means, e.g. pins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/20—Edge clamps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H23/00—Registering, tensioning, smoothing or guiding webs
- B65H23/02—Registering, tensioning, smoothing or guiding webs transversely
- B65H23/022—Registering, tensioning, smoothing or guiding webs transversely by tentering devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2793/00—Shaping techniques involving a cutting or machining operation
- B29C2793/0045—Perforating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
Definitions
- the present invention relates to an apparatus for producing a polymer film.
- the present invention relates to an apparatus for producing a polymer film, which has a characteristic tenter type film feeding processing part for heat-treating a polymer precursor film at a high temperature to give a polymer film, in the final heat treatment to produce the polymer film, and a production method of a polymer film using the apparatus.
- a film having self-supporting property which is made from a polyimide precursor such as a polyamic acid solution and the like (hereinafter to be also referred to as a green film) is imidated at a high temperature.
- the green film is heat-treated during feeding to perform drying and heat treatment.
- Such green film generally shrinks during drying.
- a tenter type feeding apparatus of a film which is what is called a tenter, is known (see patent reference 1).
- use of a tenter type feeding apparatus for the production of a polyimide film is known in many cases (see patent reference 2).
- a film feeding apparatus for drying purposes to prevent development of wrinkles in the drying step after dyeing cloth has long been known well. In addition to drying of cloth, it is also used for drying an undried plastic film while feeding in a drying step during solvent film forming method. Using a film feeding apparatus, shrinkage of a film in its width direction due to the heat during the drying•heat treatment is suppressed, whereby development of wrinkles in the film after the drying•heat treatment due to the shrinkage can be prevented.
- the film shrinks not only in the width direction of the film but omnidirectionally, since a feeding tension acts on the feeding direction of the film, it has a suppressive effect on the shrinkage. In this way, using a tenter type feeding apparatus for feeding an undried film during a drying•heat treatment, the strength and flatness necessary for the film can be ensured.
- a tenter type feeding apparatus that retains a film while stretching the film tightly in the width direction by allowing a number of pins to bite into the film along the both ends of the film is constituted by a pair of movement chains disposed in parallel, pin sheets lined up and supported thereby, and a number of pins set on the sheets.
- a feeding apparatus using pins is superior in the apparatus cost and downsizing of the apparatus because the structure is simple as compared to a feeding apparatus using clips and can be converted to a structure wherein the pathway of the feeding conveyor in a drying chamber is inverted.
- the number of the pins needs to be minimized where possible because small pieces of the film are produced as dust when the pins bite into the film.
- the apparatus has problems in that the pores made by the pins biting into the film surface are broken to form long pores in the width direction of the film when the shrinkage force of the film becomes high, and the like.
- the present invention aims at providing an apparatus suitable for producing a polymer film, which is used for producing a polyimide film wherein drying and heat treatment are performed using a tenter type feeding apparatus, which apparatus being capable of suppressing a problem of breakage of pores (made by the pins biting thereinto) to form long pores in the width direction of the film and efficiently producing a film with a superior quality, as well as a production method of a polymer film.
- the present invention aims at providing an apparatus suitable for providing a polyimide film which is a polymer film superior in the flatness and uniformity preferable for a substrate for electronic parts, and superior in the heat resistance with less warpage and curling even after a high temperature treatment, as well as a production method therefor.
- the present inventors have conducted intensive studies and found that, when a tenter type feeding apparatus is used to perform drying and a heat treatment for the production of a polymer film such as polyimide film and the like, the problem of breakage of pores (made by the pins biting thereinto) to form long pores outwardly in the width direction of the film can be suppressed by designing a means for sticking pins into the film for feeding the film by holding the both ends with the pins, and a film with a superior quality can be produced efficiently, and created an apparatus for producing a polymer film suitable for the production of a polymer film.
- the present invention provides the following constitution.
- the apparatus for producing a polymer film of the present invention deformation at a gripped portion of a film is suppressed while the film is held by the pins, and breakage of pores (made by the pins biting thereinto) to form long pores mainly in the width direction of the film can be suppressed while the pin sheets on the both ends of the film run parallel with the pin sheet on the corresponding side in a tenter type processing part (feeding apparatus) of a polymer film such as polyimide film and the like, as a result of which the distortion and uneven film thickness of the whole film can be decreased.
- a tenter type processing part feeding apparatus
- the apparatus easily produces a high quality polymer film such as polyimide film and the like, contributes to the producibility of polymer film production, and is industrially extremely effective as an apparatus for producing a polymer film as well as a production method of a polymer film.
- FIG. 1 shows an outline example of a pin sheet in the tenter type film processing machine of the present invention.
- FIG. 2 shows an outline example of the whole tenter type film processing machine of the present invention.
- FIG. 3 shows an outline example of the gripper of the tenter type film processing machine of the present invention.
- FIG. 4 shows an outline example of the gripper of a conventional tenter type film processing machine.
- FIG. 5 shows an outline of a pin sheet with a matte-processed surface to be in contact with the film, which is in the tenter type film processing machine of the present invention.
- FIG. 6 shows an outline of a pin sheet with a mirror-processed surface to be in contact with the film, which is in a conventional tenter type film processing machine.
- FIG. 7 shows an outline of a pin sheet with a riveted surface to be in contact with the film, which is in the tenter type film processing machine of the present invention.
- FIG. 8 is a schematic diagram of the outline of a pin piercing part of a tenter type film processing machine.
- FIG. 9 is a schematic diagram of the outline of one embodiment of an angular pin sheet of the tenter type film processing machine of the present invention.
- FIG. 10 is a schematic diagram of the outline of one embodiment of a pin sheet with a mechanism for controlling the depth of piercing of the pin in the tenter type film processing machine of the present invention.
- FIG. 11 shows an outline of a pin sheet with a table set on the outer side in the width direction of the pin to be in contact with the film, which is in the tenter type film processing machine of the present invention.
- FIG. 12 shows an outline of a pin sheet to be in contact with the film, which is in a conventional tenter type film processing machine.
- FIG. 13 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and the pedestal of the pin has a cavity in the tenter type film processing machine of the present invention.
- FIG. 14 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and the pedestal of the pin has a cavity in the tenter type film processing machine of the present invention.
- FIG. 15 shows a whole outline showing an outline of a pin sheet to be in contact with the film in a conventional tenter type film processing machine.
- FIG. 16 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and the pedestal of the pin and a part higher than the pin pedestal both have a cavity in the tenter type film processing machine of the present invention.
- FIG. 17 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and the pedestal of the pin has a cavity in the tenter type film processing machine of the present invention.
- FIG. 18 shows an outline of a pin sheet to be in contact with the film in a conventional tenter type film processing machine.
- FIG. 19 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and the pedestal of the pin and the table have a cavity in the tenter type film processing machine of the present invention.
- FIG. 20 shows an outline of an apparatus provided with a member for piercing the film end through a holddown pin in the tenter type film processing machine of the present invention.
- FIG. 21 shows an outline of the whole tenter type film processing machine of the present invention.
- FIG. 22 shows an outline of a preferable pin and a preferable pin sheet in the tenter type film processing machine of the present invention.
- FIG. 23 shows an outline of one embodiment of the pin and pin sheet in the tenter type film processing machine of the present invention.
- FIG. 24 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and a part higher than the pin pedestal is matte-processed in the tenter type film processing machine of the present invention.
- FIG. 25 shows an outline of a pin sheet to be in contact with a film in a conventional tenter type film processing machine.
- FIG. 26 shows an outline of a pin sheet wherein a table is provided on the outer side in the width direction of the pin to be in contact with the film and a part higher than the pin pedestal is groove-processed in the tenter type film processing machine of the present invention.
- films made from a high melting point polymer or a non-melting polymer such as polyimide, polyamideimide, cellulose acetate, polycarbonate, polyvinyl chloride, aramid and the like, and the like can be mentioned.
- These polymer films are produced by casting a solution containing such polymer, which is followed by drying and a heat treatment.
- N-methyl-2-pyrrolidone solution or N,N-dimethylacetamide solution of polyamideimide, polyamic acid, which is a polyimide precursor, or solvent-soluble polyimide, methylene chloride solution or methanol solution of cellulose acetate, methylene chloride solution or meta-cresol solution of polycarbonate, tetrahydrofuran solution of polyvinyl chloride, N-methyl-2-pyrrolidone solution of aramid and the like can be mentioned.
- the apparatus for producing a polymer film and production method of the present invention are most preferably applied to a cast film forming method using, particularly, N-methyl-2-pyrrolidone solution, N,N-dimethylacetamide solution, N,N-dimethylformamide solution and the like of polyimide and polyamic acid which is a precursor of polyimide benzoxazole.
- the polymer film of the present invention is described in detail by referring to a polyimide film as an example, which is not to be construed as limitative.
- Aromatic diamines and aromatic tetracarboxylic acids are reacted.
- Aromatic diamines and aromatic tetracarboxylic acids (anhydrides) are subjected to a (ring opening) polyaddition reaction in a solvent to give a solution of polyamic acid, which is a polyimide precursor.
- a polyimide precursor film is formed from the polyamic acid solution and the film is applied to drying•heat treatment•dehydrating condensation (imidation) to give a polyimide film.
- a polyimide film as a polymer film to which the present invention can be preferably applied is not particularly limited.
- a polyimide obtained by a combination of the following aromatic diamines and aromatic tetracarboxylic acids (anhydrides) can be recited as preferable examples.
- each isomer of amino(aminophenyl)benzoxazole is preferable.
- “each isomer” refers to each isomer determined according to the coordination sites of two amino groups possessed by amino(aminophenyl)benzoxazole (e.g., respective compounds described in the above-mentioned “Formula 1”-“Formula 4”). These diamines may be used alone or two or more kinds thereof may be used in combination.
- the aforementioned aromatic diamine having a benzoxazole structure is preferably used in 70 mol % or above.
- aromatic diamines having a diaminodiphenylether skeleton 4,4′-diaminodiphenylether (DADE), 3,3′-diaminodiphenylether and 3,4′-diaminodiphenylether and derivatives thereof can be mentioned.
- DADE 4,4′-diaminodiphenylether
- 3,3′-diaminodiphenylether and 3,4′-diaminodiphenylether and derivatives thereof can be mentioned.
- aromatic diamines having a phenylenediamine skeleton in the present invention p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and derivatives thereof can be mentioned.
- An aromatic diamine other than those mentioned above may be used.
- aromatic tetracarboxylic acids having a pyromellitic acid skeleton namely, pyromellitic acid and anhydride or halide thereof
- aromatic tetracarboxylic acids having a biphenyltetracarboxylic acid skeleton namely, biphenyltetracarboxylic acid and anhydride or halide thereof
- aromatic tetracarboxylic acid other than those mentioned above may be used.
- tetracarboxylic acids may be used alone or two or more kinds thereof may be used in combination.
- the solvent to be used when aromatic diamines and aromatic tetracarboxylic anhydrides are polymerized to give polyamic acid is not particularly limited as long as it dissolves both a monomer to be the starting material and the polyamic acid produced.
- a polar organic solvent is preferable and, for example, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric amide, ethylcellosolve acetate, diethyleneglycol dimethylether, sulfolane, halogenated phenols and the like can be used.
- N-methyl-2-pyrrolidone and N,N-dimethylacetamide are preferably applied.
- These solvents can be used alone or in a mixture.
- the amount of the solvent to be used may be an amount sufficient to dissolve a monomer to be the starting material.
- a specific amount used is such an amount that renders the mass of the monomer in a solution dissolving the monomer generally 5-40% by mass, preferably 10-20% by mass.
- the conditions of the polymerization reaction to give the aforementioned polyamic acid may be conventionally known conditions. Specific examples thereof include continuous stirring and/or mixing in an organic solvent within a temperature range of 0-80° C. for 10 min-30 hr. Where necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of addition of both monomers is not particularly limited, but aromatic tetracarboxylic anhydrides are preferably added to a solution of aromatic diamines.
- the mass of polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5-40% by mass, more preferably 10-30% by mass, and the viscosity of the aforementioned solution as measured by a Brookfield viscosimeter (25° C.) is preferably 10-2000 Pa ⁇ s, more preferably 100-1000 Pa ⁇ s, from the aspect of feeding stability.
- the reduced viscosity ( ⁇ sp/C) of the polyamic acid in the present invention is not particularly limited, not less than 3.0 dl/g is preferable, not less than 4.0 dl/g is more preferable, and not less than 5.0 dl/g is still more preferable.
- a small amount of a terminal sealing agent may be added to aromatic diamines before the polymerization reaction to control the polymerization.
- a compound having a carbon-carbon double bond such as maleic anhydride and the like can be mentioned.
- the amount of maleic anhydride when it is used is preferably 0.001-1.0 mol per 1 mol of aromatic diamines.
- Vacuum defoaming during the polymerization reaction is effective for producing a polyamic acid solution with good quality.
- removal of air bubbles and dissolved gas in the solution in advance by a treatment such as reduction of pressure and the like is also an effective treatment to afford the polyimide film in the present invention.
- a polyamic acid solution is applied to a support to form a film.
- the support to which a polyamic acid solution is applied only needs to have smoothness and rigidity of the level sufficient to form a film from the polyamic acid solution.
- a drum-like or belt-like rotator with a surface made of a metal, plastic, glass, porcelain and the like, and the like can be mentioned.
- the surface of a support is preferably a metal, more preferably stainless which is rust-free and superior in the corrosion resistance.
- the surface of the support may be plated with a metal such as Cr, Ni, Sn and the like. Where necessary, the surface of the support may be a mirror- or matte-processed. Furthermore, the amount of air and temperature during drying may be appropriately selected and employed depending on difference in the support. For coating of a support with a polyamic acid solution, casting from a slit spinneret, extrusion from an extruder, squeeze coating, reverse coating, die coating, applicator coating, wirebar coating and the like may be used. The method is not limited to these and conventionally-known solution application means can be appropriately used.
- the film-like polyamic acid solution is dried to the level exhibiting the self-supporting property to give a polyimide precursor film (also referred to as a green film), which is treated at a high temperature to allow imidation to give a polyimide film.
- a polyimide precursor film also referred to as a green film
- a method for imidating a green film a method including carrying out an imidation reaction by applying a heat treatment using a polyamic acid solution free of a cyclization (imidation) catalyst and a dehydrating agent (what is called a thermal cyclization method) and a chemical cyclization method wherein an imidation reaction is performed by the action of a cyclization catalyst and dehydrating agent in a polyamic acid solution containing them can be mentioned.
- the temperature of the heat treatment in the thermal cyclization method is preferably 150-500° C.
- the temperature of the heat treatment is lower than this range, sufficient cyclization becomes difficult. When it is higher than this range, the degradation proceeds and the film tends to be brittle.
- a more preferable embodiment is, for example, a two-stage heat treatment step including an initial stage heat treatment for treating at 150-250° C. for 3-20 min and a latter stage heat treatment for treating with heat at 350-500° C. for 3-20 min.
- a polyamic acid solution is applied to a support, an imidation reaction is partially carried out to form a self-supportive film, and then the imidation is completely performed by heating.
- the condition for partial imidation reaction is a heat treatment preferably at 100-200° C. for 3-20 min.
- the condition for complete imidation reaction is a heat treatment preferably at 200-400° C. for 3-20 min.
- the timing of addition of a cyclization catalyst to a polyamic acid solution is not particularly limited, and the catalyst may be added in advance prior to the polymerization reaction to give polyamic acid.
- the cyclization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine and the like, heterocyclic tertiary amines such as isoquinoline, pyridine, beta-picoline and the like, and the like. Of these, at least one kind of amine selected from heterocyclic tertiary amines is preferable. While the amount of the cyclization catalyst to be used relative to 1 mol of polyamic acid is not particularly limited, it is preferably 0.5-8 mol.
- the timing of addition of a dehydrating agent to a polyamic acid solution is not particularly limited, and the dehydrating agent may be added in advance prior to the polymerization reaction to give polyamic acid.
- the dehydrating agent include aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride and the like, aromatic carboxylic anhydrides such as benzoic anhydride and the like, and the like. Of these, acetic anhydride, benzoic anhydride and a mixture thereof are preferable.
- the amount of the dehydrating agent to be used relative to 1 mol of polyamic acid is not particularly limited, it is preferably 0.1-4 mol. When a dehydrating agent is used, a gelling retardant such as acetylacetone and the like may be used in combination.
- the thickness of the polymer film is not particularly limited, it is 5-150 ⁇ m, preferably 10-100 ⁇ m, in consideration of use as a base substrate for the printed circuit board mentioned below.
- the film thickness can be easily controlled by the amount of the polyamic acid solution to be applied to a support and the concentration of the polyamic acid solution.
- the slip property of a polymer film is preferably improved by adding a lubricant to polyimide and the like to form ultrafine concaves and convexes on the film surface.
- inorganic or organic fine particles having an average particle size of about 0.03 ⁇ m-3 ⁇ m can be used.
- specific examples thereof include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogenphosphate, calcium pyrrophosphate, magnesium oxide, calcium oxide, clay mineral and the like.
- the apparatus for producing a polymer film of the present invention comprises a tenter type processing part wherein film ends are held at the both ends in the width direction of the film, which is constituted with a number of pin sheets and a number of pins provided for individual pin sheets, by piercing the both ends of the film with the pins, and the film is fed while being stretched tightly in the width direction and/or the feeding direction (hereinafter to be also referred to as a pin tenter), and has a means to suppress deformation of the film in the vicinity of the pins at the time point when the film is fed with the pins piercing the both ends of the film.
- a tenter type processing part wherein film ends are held at the both ends in the width direction of the film, which is constituted with a number of pin sheets and a number of pins provided for individual pin sheets, by piercing the both ends of the film with the pins, and the film is fed while being stretched tightly in the width direction and/or the feeding direction (hereinafter to be also referred to
- a means to cool the pin temperature to less than 180° C. can be preferably applied, for example, in the drying or imidation step for the production of a polyimide film. Particularly, it is preferably applied in the step of imidation of a green film by a heat treatment.
- a green film is heat-treated in a pin tenter, the both ends in the width direction of the film are held by sticking the film with pins, and the film is fed while being stretched tightly in the width direction and/or the feeding direction and subjected to imidation in a tenter heat treatment furnace.
- the lower limit of the pin temperature is not particularly present, when it is too low, dew drops may attach to the pins or the temperature distribution in the tenter may become large. Thus, not less than 30° C. is suitable.
- a pin cooling means which is one of the preferable embodiments of the present invention, is described in detail.
- a tenter using such pin as a film-fixing means is referred to as a pin tenter.
- the pin sheets for the pin tenter are combined with, for example, general driving chains shown in FIGS. 1 , 2 and set as a caterpillar track.
- Known driving chains of the pin tenter include a type wherein the chain passes in a treatment furnace for both ways, and a type wherein the chain passes outside the treatment pathway for the homeward way.
- a type wherein the chain passes in a treatment furnace for both ways is preferably employed. This type enables downsizing of the whole apparatus to a compact one.
- a number of pin sheets provided with a number of pins are arranged on both ends of a film.
- the individual pin sheets have plural pins serially arranged on the innermost side in the feeding direction and other plural pins. These pins feed the film by holding the both ends thereof.
- these plural pin sheets run in parallel to each other on both ends of the film and maintained at an extremely high temperature to allow heat treatment of the film.
- the pins and pin sheets are exposed to the high temperature at least in this treatment chamber. After completion of the heat treatment of the film, the pin turns and returns to the original position where it holds a new film.
- the pin and pin sheet are preferably cooled between the return path of the driving chain on the entry side of the treatment path and the pinning zone.
- Conventional tenter type feeding apparatuses do not have a means to cool pins and pin sheets after heating to a heat treatment temperature of, for example, 450° C., and the high temperature is maintained at the time point when the both ends of the film are held and the feeding is started.
- a heat treatment temperature for example, 450° C.
- uniformity of film holding is difficult to maintain, expansion of pores (made by the pins biting thereinto) in the width direction or feeding direction of the film and breakage easily occur, the film as a whole shows increased distortion, and the uneven film thickness expands.
- a cooling means is provided at a part immediately before the pins after completion of the film heat treatment turn and return to the position to hold the film, whereby the pins are cooled to lower than 180° C. Consequently, the pins are sufficiently cooled at the film holding start time point, and the uniformity of film holding can be maintained during piercing of the both ends of the film with the pins, expansion of pores in the width direction of the film or feeding direction from the pores into which the pins bite and occurrence of breakage can be suppressed, the distortion of the film as a whole can be decreased, and the uneven film thickness can be decreased.
- any of air cooling and water cooling can be used, and a cooling medium other than air and water can also be used. From the aspect of cooling efficiency, a liquid cooling medium is preferably used. Moreover, considering that the tenter itself is heated to the fire point or above of a conventional organic solvent, a cooling means by water cooling is most preferable. To prevent dew drops near the cooling part, dew point control of the atmosphere and cold air when using air as a cooling medium is preferable.
- One of the preferable embodiments of the apparatus for producing a polymer film of the present invention is one wherein individual pins arranged on the innermost side in the film width direction in a pin tenter are all provided at equal intervals in the film feeding direction in individual pin sheets as well as between other pin sheets.
- the pin arrangement is described in detail.
- a number of pin sheets provided with a number of pins are arranged on both ends of a film, the individual pin sheets have plural pins serially arranged on the innermost side in the feeding direction and other plural pins, the arrangement of the aforementioned individual pin sheets having plural pins serially arranged on the innermost side in the feeding direction is important.
- the plural pins serially arranged in the feeding direction on the innermost side of the individual pin sheets are, for example, A 1 , A 2 , A 3 , A 4 . . .
- An in the feeding direction, and the plural pins serially arranged in the feeding direction on the innermost side of the adjacent pin sheets are, for example, B 1 , B 2 , B 3 , B 4 . . . Bn in the feeding direction, the intervals between respective pins of A 1 , A 2 , A 3 , A 4 . . . An and B 1 , B 2 , B 3 , B 4 . . . Bn are substantially the same.
- the distance between An and B 1 is also substantially the same as the former, and the aforementioned relationship can be found in plural pins serially arranged on the innermost side in the feeding direction in other pin sheets.
- the plural pin sheets run parallel to each other at the both ends of the film in the treatment chamber, where the aforementioned pin intervals are maintained and the film is held and fed as long as the plural pin sheets run parallel to each other at the both ends of the film at least in this treatment chamber.
- the pin intervals are preferably not more than 1/10 relative to the width of the film being held. This suppresses the deformation of the film in the vicinity of the pin. As a result, the uniformity of film holding can be easily maintained, expansion of pores in the width direction of the film or in the feeding direction from the pores into which the pins bite and occurrence of breakage can be suppressed, the distortion of the film as a whole can be decreased, and the uneven film thickness can be decreased.
- a preferable embodiment of the apparatus for producing a polymer film of the present invention is an apparatus for producing a polymer film comprising a tenter type processing part wherein film ends are held at the both ends in the width direction of the film, which is constituted with a number of pin sheets and a number of pins provided for individual pin sheets, by piercing the both ends of the film with the pins, and the film is fed while being stretched tightly in the width direction and/or in the feeding direction, and concave and convex of a maximum amplitude of 5-5000 ⁇ m are formed at least on the surface of the side of the pin sheet to be in contact with the pierced film.
- the shape and size of the concave and convex having a maximum amplitude of 5-5000 ⁇ m is not particularly limited as long as it can suppress welding and heat conduction between the film and the contact surface of the pin sheet, as well as deformation of the film in the vicinity of the pin.
- the preferable pin sheets are shown, for example, in FIG. 5 and FIG. 7 .
- a means for piercing the both ends of the film by pins using a hold down brush roll as shown in FIG. 8 is preferably employed.
- a member with a brush made of a bristle material made from a material having a melting point or softening point of not less than 150° C. and an elastic modulus of not less than 4 GPa is preferably used to have the film end pierced by the pin.
- a brush roll with a brush provided on the periphery of the cylindrical flat plane can be preferably used.
- a brush made of a bristle material made from a material having a melting point or softening point of not less than 150° C. and an elastic modulus of not less than 4 GPa is preferable because it can afford uniform piercing of the film due to such property, and degradation of the function is extremely small after using for a long time.
- polymer fiber, carbon fiber, glass fiber and the like having a high elastic modulus can be mentioned. More preferably, it is a polymer material such as polymer fiber and the like, aromatic polyamide, for example, Conex (manufactured by TEIJIN LIMITED) and the like can be mentioned.
- a preferable embodiment of the apparatus for producing a polymer film of the present invention is an apparatus for producing a polymer film comprising a tenter type processing part wherein film ends are held at the both ends in the width direction of the film, which is constituted with a number of pin sheets and a number of pins provided for individual pin sheets, by piercing the both ends of the film with the pins, and the film is fed while being stretched tightly in the width direction and/or in the feeding direction, and the angle of planting the pins in the pin sheet is 0.5-15 degrees toward the outer side of the width direction of the film relative to the perpendicular direction of the pin sheet.
- it has a slant of 1-10 degrees, more preferably about 2-7 degrees.
- a constitution afforded by controlling the protrusion height in a structure wherein protrusions are formed on the pin sheet and pressing down depth of the film is controlled when it hits the protrusion.
- Such protrusion can be formed by planting rivets and the like in, for example, a pin sheet shown in FIG. 10 , where the protrusion height may be about 2-70%, preferably about 10-40%, of the pin height.
- the protrusion height may be about 2-70%, preferably about 10-40%, of the pin height.
- the film may contact the pin sheet in some parts, which in turn may sometimes cause welding of the film and the pin sheet and the like.
- the protrusion is too high, piercing depth becomes insufficient and the film may be released from the pins.
- the film can be pierced with the pin by pressing down the film onto the pin with a pressing tool.
- the pressing down depth may be set to a middle part of the pin, whereby the piercing depth of the film can be preferably adjusted.
- the setting position of the brush roll is adjusted to set the tip of the brush roll to a certain distance from the surface of the pin sheet, whereby the piercing depth of the film can be controlled.
- a preferable embodiment of the apparatus for producing a polymer film of the present invention is use of a pin sheet having, on the outer side relative to the width direction, a part higher than a pedestal provided with the pins of pin sheets (pin pedestal), so that the film will not come into contact with the pin pedestal. It can suppress welding and heat conduction between the film and the surface of the pin sheet to be in contact therewith, whereby deformation of the film in the vicinity of the pin can be suppressed.
- the shape of the part higher than the pedestal, which is set on the outer side relative to the width direction of the pin sheet is not particularly limited as long as it is positioned higher than the pin pedestal where pins are planted, thereby functioning to prevent the film from coming into contact with the pin pedestal.
- the table may contact the film only at the outer side in the width direction of the pin sheet where pins are not planted and which is made to have a greater height.
- the pin pedestal of the pin sheet may have a slant toward the outer side in the width direction.
- the shape and size thereof are preferably that (1) the height of the table is lower than the pin tip by the range of 3-8 mm. More preferably, it is lower by the range of 4-6 mm.
- the height of the table is lower than the pin tip by less than 3 mm, the depth of the pins piercing the both ends of the film is shallow, the film is unpreferably detached frequently from the pins during the subsequent heat treatment step.
- the height of the table is lower than the pin tip by not less than 8 mm, it unpreferably causes a great resistance in removing the film from the pin sheets after the heat treatment, which may lead to tearing of the both ends of the film in the worst case.
- the height of the table is preferably greater by the range of 1-5 mm than that of the pedestal where the pins are set. More preferably, it is higher by the range of 2-3 mm.
- the periphery of the table is preferably chamfered. Without a chamfer processing, the film in contact with the periphery of the table is preferably torn.
- the pedestal provided with the pins preferably has a cavity.
- This has a direct heat transfer suppressive effect from the pin sheet to the film.
- the cavity area in the pin pedestal is preferably 10-50% of the whole pin pedestal provided with the pins. When it is less than 10%, the effect thereof is hardly expressed and, when it exceeds 50%, the mechanical stability of the pin sheet per se, such as maintenance of flatness and the like, shows unpreferable phenomena.
- a preferable embodiment of the apparatus for producing a polymer film of the present invention is one wherein a cavity in the width direction is formed in a part higher than the pin pedestal provided on the outer side in the width direction of the pin sheet. It has a direct heat transfer suppressive effect from the part higher than the pin pedestal to the film and deformation of the film in the vicinity of the pin can be suppressed. As a result, the temperature difference between the film center portion and the gripped portion and difference in the breaking strength during film feeding become small, which is effective for the prevention of troubles such as film breakage and the like in the tenter.
- the total sectional area of the cavity formed in the part higher than the pin pedestal provided on the outer side in the width direction of the pin sheet is preferably 20-80% of the total sectional area of the part higher than the pin pedestal provided on the outer side in the width direction of the pin sheet.
- it is less than 20%, its effect is hardly expressed and, when it exceeds 80%, the mechanical stability of the pin pedestal per se provided on the outer side in the width direction of the pin sheet, such as maintenance of the distance between the film and the pin pedestal and the like, shows unpreferable phenomena.
- a preferable embodiment of the apparatus for producing a polymer film of the present invention is an apparatus comprising a pin sheet having, on the outer side relative to the width direction, a part higher than a pin pedestal, wherein the distance between the part and the pin arranged at the outermost part in the width direction on the pedestal of the pin sheet is 2-10 mm, and a pin density (P) satisfying the following formula (1): 2/( t+ 70) ⁇ P ⁇ 8/( t+ 70) (1) wherein t is a film thickness ( ⁇ m) after tenter processing, and P is a density (pins/mm 2 ) of the pins relative to the total area of the pedestal provided with the pins other than the table provided on the outer side relative to the width direction of the pin sheet (a part higher than the pin pedestal).
- a pin sheet having, on the outer side relative to the width direction, a part higher than a pedestal provided with the pins of pin sheets (pin pedestal), so that the film will not come into contact with the pin pedestal, welding and heat conduction between the film and the surface of the pin sheet to be in contact therewith can be suppressed, whereby deformation of the film in the vicinity of the pin can be suppressed.
- the distance between the part higher than the pin pedestal provided on the outer side relative to the width direction of the pin sheet and the pin arranged at the outermost part in the width direction on the pedestal of the pin sheet is less than 2 mm
- the vicinity of pin piercing provided at the outermost part in the width direction contacts the part higher than the pin pedestal provided on the outer side relative to the width direction of the pin sheet. Therefore, the film sometimes tends to tear easily during detachment of the film from the pin sheets after a heat treatment.
- the film when the thickness is particularly small, the film is sometimes easily torn, which is unpreferable.
- P when P is greater than 8/(t+70), the distance between adjacent pins becomes narrow, and therefore, the film sometimes tends to tear easily during detachment of the film from the pin sheets after the heat treatment.
- a more preferable embodiment is the above-mentioned apparatus for producing a polymer film, wherein, as the longitudinal arrangement of the pins to be provided on the pin pedestal, the distance L M (mm) of the adjacent pins relative to the feeding direction of the pin sheet is 2-8 times the diameter d (mm) of the pins for piercing the film, and the pin sheet comprises at least two rows of pin longitudinal arrangements.
- the pin sheet comprises only one row of pin longitudinal arrangement
- the pin sheet pedestal and the film are subjected to a contactless heat treatment at a high temperature for prevention of welding of the film and the pin sheet and the like.
- a heat shrink stress on the pin vicinity increases or the film is greatly influenced by curling at the outermost end portions.
- the film is sometimes easily torn, which is unpreferable.
- the film ends are preferably held on pin sheets such that the position of the end in the width direction of the film will be 5-25 mm outside the outermost part in the width direction of the pins provided on the pin sheets.
- the ear portion is unpreferably torn during detachment of the film from the pin sheets after the heat treatment, which is due to deformation such as curling and the like developed to become resistance by the heat shrinkage at the outermost end in the film width direction.
- the shape of the part higher than the pin pedestal provided on the outer side relative to the width direction of the pin sheet is not particularly limited as long as it is positioned higher than the pin pedestal where pins are planted, thereby functioning to prevent the film from coming into contact with the pin pedestal.
- the table may contact the film only at the outer side in the width direction of the pin sheet where pins are not planted and which is made to have a greater height.
- the pin pedestal of the pin sheet may have a slant toward the outer side in the width direction.
- the shape and size thereof are preferably that (1) the height of the table is lower than the pin tip by the range of 3-8 mm. More preferably, it is lower by the range of 4-6 mm.
- the height of the table is lower than the pin tip by less than 3 mm, the depth of the pins piercing the both ends of the film is shallow, the film is unpreferably detached frequently from the pins during the subsequent heat treatment step.
- the height of the table is lower than the pin tip by more than 8 mm, it unpreferably causes a great resistance in removing the film from the pin sheets after the heat treatment, which may lead to tearing of the both ends of the film in the worst case.
- the gripped portion in the pin tenter of the present invention is constituted by a number of pin sheets and a number of pins provided on individual pin sheets.
- the wind speed in the heat treatment furnace is preferably from 0.1 m/sec to 3.0 m/sec.
- the wind speed in the heat treatment furnace is preferably not more than 3 m/sec, more preferably 2 m/min.
- the lower limit of the wind speed in the present invention is 0.1 m/sec, preferably about 0.3 m/sec.
- the air pressure is preferably applied uniformly from the both surfaces of the film held in the present invention.
- the film When the wind speed exceeds a given range, or the air pressure from the both surfaces of the film is nonuniform, the film may be released from the pins, or the film may be pressed down more than necessary to contact the pin sheets, whereby the film is heated by the pin sheets more than necessary to cause film breakage and the like.
- the wind speed is less than the lower limit, renewal of the atmosphere of the film surface becomes insufficient, whereby progress of the desired drying and chemical reactions in the heat treatment furnace may be prevented unpreferably.
- a solution of a polymer dissolved in N-methyl-2-pyrrolidone (or N,N-dimethylacetamide) to a concentration of 0.2 g/dl was measured with a Ubbelohde viscosity tube at 30° C. (When the solvent used for preparation of the polyamic acid solution was N,N-dimethylacetamide, the polymer was dissolved therein and measured.)
- the thickness was measured using a micrometer (manufactured by FEINPRUF, Millitron 1254D).
- a polyimide film to be the measurement target was cut out in the machine direction (MD direction) and the transverse direction (TD direction) in a 100 mm ⁇ 10 mm rectangular strip and used as a test piece.
- MD direction machine direction
- TD direction transverse direction
- tensile tester manufactured by Shimadzu Corporation, Autograph (trade name), name: AG-5000A
- tensile modulus, tensile strength at break and tensile elongation at break were measured under the conditions of tensile rate (50 mm/min), distance between chucks (40 mm) in both MD direction and TD direction.
- the tensile modulus in the length direction of the bristle material forming the brush was also measured in the same manner.
- the measurement target film was measured for the expansion and/or contraction rate in the MD direction and TD direction under the following conditions, the expansion and/or contraction rate/temperature was measured at 15° C. intervals of 30° C.-45° C., 45° C.-60° C. and so on, the measurement was performed up to 300° C. and an average of all measurement values was calculated as CTE.
- the MD direction and TD direction mean the same as in the measurement of the above-mentioned “3.”.
- the measurement target film was subjected to differential scanning calorimetry (DSC) under the following conditions, and the melting point (melting peak temperature Tpm) and glass transition point (Tmg) were determined according to JIS K 7121.
- Tpm melting peak temperature
- Tmg glass transition point
- the measurement target film was thoroughly dried and used as a sample.
- the sample was subjected to a thermogravimetric analysis (TGA) under the following conditions, and the temperature at which the sample mass decreased by 5% was taken as a thermal decomposition temperature.
- TGA thermogravimetric analysis
- the surface roughness was measured using a surface roughness tester HANDYSURF E-35A (manufactured by TOKYO SEIMITSU CO., LTD.).
- Amorphous silica spherical particles SEAHOSTAR KE-P10 manufactured by NIPPON SHOKUBAI CO., LTD., 1.22 parts by mass
- N-methyl-2-pyrrolidone 420 parts by mass
- SEAHOSTAR KE-P10 manufactured by NIPPON SHOKUBAI CO., LTD., 1.22 parts by mass
- N-methyl-2-pyrrolidone 420 parts by mass
- a container in which a part in contact with a liquid and an infusion piping were made of austenite stainless steel SUS316L and stirred with homogenizer T-25 Basic (manufactured by IKA Labor technik) at 1000 rpm/min for 1 min to give a predispersion liquid.
- the average particle size in the predispersion liquid was 0.11 ⁇ m.
- Amorphous silica spherical particles SEAHOSTAR KE-P10 manufactured by NIPPON SHOKUBAI CO., LTD., 7.6 parts by mass
- N-methyl-2-pyrrolidone (390 parts by mass) were placed in a container in which a part in contact with a liquid and an infusion piping were made of austenite stainless steel SUS316L and stirred with homogenizer T-25 Basic (manufactured by IKA Labor technik) at 1000 rpm/min for 1 min to give a predispersion liquid.
- Amorphous silica spherical particles SEAHOSTAR KE-P10 manufactured by NIPPON SHOKUBAI CO., LTD., 3.7 parts by mass
- N-methyl-2-pyrrolidone 420 parts by mass
- the polyamic acid solutions obtained in Reference Examples 1-4 were applied to a lubricant-free surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) with a comma coater (gap 150 ⁇ m, coating width 1240 mm), and dried at 90° C. for 60 min. After drying, the self-supportive polyamic acid film was released from the support and cut at both ends to give each green film with thickness 21 ⁇ m, width 1200 mm.
- the film feeding condition was good, and release from the pins did not occur in the tenter.
- the film tear width in the pin piercing part at the tenter outlet was within about 1 mm.
- the obtained film was cooled to room temperature, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 1-4.
- the measurement results such as property and the like of the obtained polyimide films are shown in Table 1.
- the length of the pin sheet was 65.0 mm, and the pin distance was 7.0 mm.
- the obtained film was spread on a surface plate with a clean surface, and an uneven film end producing a space between the film and the surface plate was taken as a flatness failure.
- the both ends of the film were cut until the film end did not rise from the surface of the surface plate and the whole film came into close contact with the surface plate.
- the film width at that time was defined as an effective width.
- the film forming and evaluation were performed in the same manner as in Example 1. However, in the Comparative Examples, the pins and the pin sheets were not cooled. During film forming, the temperature of the pins and the pin sheets changed in the range of about 205° C. ⁇ 12° C.
- Example 1 Thereafter, in the same manner as in Example 1, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Comparative Examples 1-4.
- the results such as property and the like of the obtained polyimide films are shown in Table 1.
- the green films (thickness 21 ⁇ m, width 1200 mm) obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4 were passed through a pin tenter having pin sheets with pins arranged thereon so that the distance between the pins will be uniform when, as shown in FIG. 3 , the pin sheets are lined up.
- the distance between the pin sheets was 1140 mm, or 30 mm each of the both ends of the green film was pierced with the pins, and the film was subjected to two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) to allow an imidation reaction to proceed.
- the film was cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 13-16.
- the measurement results such as property and the like of the obtained polyimide films are shown in Table 3.
- the length of the pin sheet was 65.0 mm, and the pin distance was 7.0 mm.
- the green films obtained in the same manner as in Example 13 were held at the both ends in the pin tenter containing pin sheets, as shown in FIG. 4 , and heat-treated under the conditions as in Example 13, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Comparative Examples 5-8.
- the results such as property and the like of the obtained polyimide films are shown in Table 3.
- the length of the pin sheet was 63.0 mm, the pin distance was 7.0 mm and the distance between pins of pin sheets was 14.0 mm.
- the green films obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4 were held by inserting pins into the holes made in the films and subjected to a heat treatment in the tenter.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height was 12 mm and the distance between pin sheets was 1140 mm.
- the matte processing was performed by a sandblast treatment, where the surface roughness Ra was 11.5 ⁇ m.
- the setting of the heat treatment of the tenter was as follows. A two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) was applied to allow an imidation reaction to proceed. Thereafter, the film was cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 17-20. The feeding state during heat treatment and the measurement results such as property and the like of the obtained polyimide films are shown in Table 4.
- Example 17 The green films obtained in the same manner as in Example 17 were held at the both ends in a pin tenter wherein needle pins were planted on the surface of the mirror-processed pin sheets, as shown in FIG. 6 , heat-treated under the conditions as in Example 17, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Comparative Examples 9-12.
- the feeding state during heat treatment and the results such as property and the like of the obtained polyimide films are shown in Table 4. Ra of the surface of the surface-processed pin sheets was 0.13 ⁇ m.
- the polyamic acid solutions obtained in Reference Examples 1-4 were applied to a stainless steel endless belt with a die coater (coating width 1240 mm), and dried at 110° C. for 40 min. After drying, the self-supportive polyamic acid film was released from the support and cut at both ends to give each green film with thickness 43 ⁇ m, width 1200 mm.
- Green films (thickness 21 ⁇ m, width 1200 mm) were obtained in the same manner as in Example 1 from the polyamic acid solution obtained in Reference Example 1.
- the green films of Comparative Examples 13-17 were held by inserting pins into the films and subjected to a heat treatment in the tenter.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, the distance between pin sheets was 1140 mm.
- the aforementioned brush roll made by Conex was provided with a micrometer permitting adjustment of the height, so that the tip of bristle can have some distance from the pin sheet surface. In these Examples, it was adjusted to be set at 3 mm from the pin sheet. The films were pressed down nearly to that position, and held floating from the pin sheets.
- the setting of the heat treatment in the tenter was as follows. A two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) was applied to allow an imidation reaction to proceed. The maximum wind speed in the tenter was 0.5 m/sec.
- the width of the pins on both ends was shortened by 2%, i.e., 98% of the initial width.
- the pin width was slightly widened to 99% of the initial width, widened to 102% in the temperature rise period, and further widened up to the middle point of the second stage to 103%, whereafter the films were treated at a constant width. Thereafter, the films were cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of plural Example 25 and Comparative Example 13.
- Example 25 release from the pin did not occur during the treatment, the distance between the pin sheet and the film was almost the same as that at the initial stage of pin piercing and the running state was also good. However, in Comparative Example 13, release from the pin occurred during the treatment, and problems of fluttering and the like were developed during running.
- the wind speed in the Tables was measured using “Anemomaster 24-6111” (manufactured by KANOMAX), where the detection part thereof was placed right beneath the wind blast outlet for the measurement.
- “Anemomaster 24-6111” manufactured by KANOMAX
- the values obtained by operation of air blast system and driving system at ambient temperature were used. This is because use at a high temperature is problematic in view of the heat resistance of the wind speed detection part.
- the air blast system was controlled in compliance with the control during measurement at ambient temperature, and the value from the air blast system control value during the aforementioned measurement at ambient temperature was used for the actual wind speed.
- the green films (thickness 21 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 21 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the green films (thickness 21 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 21 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the film does not stick to the pin sheet, stable feeding is possible, the film can be released smoothly from the pin sheet, the film can be fed stably to prevent easy tearing and breakage of the film, film forming with a wide effective width and less uselessness is enabled, and the obtained film is superior in the quality in the width direction and uniformity in the film thickness.
- the green films (thickness 21 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- the setting of the heat treatment in the tenter was as follows. A two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) was applied to allow an imidation reaction to proceed. Thereafter, the film was cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 36-39. The feeding state during heat treatment and the measurement results such as property and the like of the obtained polyimide films are shown in Table 8.
- the obtained film was spread on a surface plate with a clean surface, and an uneven film end producing a space between the film and the surface plate was taken as a flatness failure.
- the both ends of the film were cut until the film end did not rise from the surface of the surface plate and the whole film came into close contact with the surface plate.
- the film width at that time was defined as an effective width.
- the green films were each obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the green films (thickness 43 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 21 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height from the pin pedestal was 8 mm, the height of the table set at the outer side in the width direction of the pin sheet was 3 mm higher than the pin pedestal and 5 mm lower than the pin tip, and the distance between pin sheets was 1140 mm.
- the length in the longitudinal direction of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- cavities corresponding to 29% of the whole pin pedestal were formed between pins on the pin pedestal.
- the green films (thickness 21 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- cavities corresponding to 25% of the whole pin pedestal were formed between pins on the pin pedestal.
- the setting of the heat treatment in the tenter was as follows. A two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) was applied to allow an imidation reaction to proceed. Thereafter, the film was cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 44-47. The feeding state during heat treatment and the measurement results such as property and the like of the obtained polyimide films are shown in Table 9.
- the obtained film was spread on a surface plate with a clean surface, and an uneven film end producing a space between the film and the surface plate was taken as a flatness failure.
- the both ends of the film were cut until the film end did not rise from the surface of the surface plate and the whole film came into close contact with the surface plate.
- the film width at that time was defined as an effective width.
- the width of film tearing at pin portion was measured with a scale at about 10 m from the top of the film.
- the green films were each obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the green films (thickness 43 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 21 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height from the pin pedestal was 8 mm, the height of the table set at the outer side in the width direction of the pin sheet was 3 mm higher than the pin pedestal and 5 mm lower than the pin tip, and the distance between pin sheets was 1140 mm.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- cavities corresponding to 29% of the whole pin pedestal were formed between pins on the pin pedestal.
- cavities corresponding to 38% of the whole sectional area were formed in the table set at the outer side in the width direction of the pin sheet.
- the green films were each obtained in the same manner as in Example 1 except the film thickness, from the polyamic acid solutions obtained in Reference Examples 1-4.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- the distance between the table set at the outer side in the width direction of the pin sheet and the pins provided on the pin sheets and arranged at the outermost part in the width direction was 2.5 mm.
- cavities corresponding to 14% of the whole pin pedestal were formed between pins on the pin pedestal.
- the shortest distance L t between the adjacent pins was 4.5 mm relative to the width direction of the pin sheets
- the pin arrangements were 4 rows relative to the feeding direction of the pin sheets
- the distance L M of the adjacent pins was 5.2 mm
- the diameter d of the pins piercing the film was 1.0 mm.
- the density of the pins relative to the total area of the pedestal provided with the pins was 0.038 pin/mm 2 .
- the setting of the heat treatment in the tenter was as follows. A two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) was applied to allow an imidation reaction to proceed. Thereafter, the film was cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 52-55. The feeding state during heat treatment and the measurement results such as property and the like of the obtained polyimide films are shown in Table 10.
- the obtained film was spread on a surface plate with a clean surface, and an uneven film end producing a space between the film and the surface plate was taken as a flatness failure.
- the both ends of the film were cut until the film end did not rise from the surface of the surface plate and the whole film came into close contact with the surface plate.
- the film width at that time was defined as an effective width.
- the width of film tearing at pin portion was measured with a scale at about 10 m from the top of the film.
- the green films were each obtained in the same manner as in Example 1 except the film thickness, from the polyamic acid solutions obtained in Reference Examples 1-4.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height from the pin pedestal was 8 mm, the height of the table set at the outer side in the width direction of the pin sheet was 0.5 mm higher than the pin pedestal and 7.5 mm lower than the pin tip, and the distance between pin sheets was 1140 mm.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 40 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- the distance between the table set at the outer side in the width direction of the pin sheet and the pins provided on the pin sheets and arranged at the outermost part in the width direction was 11.0 mm.
- the shortest distance L t between the adjacent pins was 6.4 mm relative to the width direction of the pin sheets
- the pin arrangements were 3 rows relative to the feeding direction of the pin sheets
- the distance L M of the adjacent pins was 11.0 mm
- the diameter d of the pins piercing the film was 1.0 mm.
- the density of the pins relative to the total area of the pedestal provided with the pins was 0.014 pin/mm 2 .
- the green films (thickness 6 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 21 except the film thickness, from the polyamic acid solutions obtained in Reference Examples 1-4.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height from the pin pedestal was 8 mm, the height of the table set at the outer side in the width direction of the pin sheet was 3 mm higher than the pin pedestal and 5 mm lower than the pin tip, and the distance between pin sheets was 1140 mm.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- the distance between the table set at the outer side in the width direction of the pin sheet and the pins provided on the pin sheets and arranged at the outermost part in the width direction was 3.5 mm.
- cavities corresponding to 14% of the whole pin pedestal were formed between pins on the pin pedestal, and cavities corresponding to 38% of the whole sectional area were formed in the table set at the outer side in the width direction of the pin sheet.
- the shortest distance L t between the adjacent pins was 3.5 mm relative to the width direction of the pin sheets
- the pin arrangements were 4 rows relative to the feeding direction of the pin sheets
- the distance L M of the adjacent pins was 5.2 mm
- the diameter d of the pins piercing the film was 1.0 mm.
- the density of the pins relative to the total area of the pedestal provided with the pins was 0.038 pin/mm 2 .
- the green films (thickness 21 ⁇ m, width 1200 mm, length 1000 m) were each obtained in the same manner as in Example 1 from the polyamic acid solution obtained in Reference Example 1.
- a strip brush (channel width 5 mm, channel height 5 mm, bristle length 25 mm, total height 30 mm) using Conex (manufactured by TEIJIN LIMITED, aromatic polyamide rod, diameter 0.2 mm ⁇ ) as a bristle material was prepared.
- the strip brush was processed into an outer radius brush (outer shape 160 mm, inner diameter 100 mm, width 40 mm).
- Four of the same outer radius brushes were produced and used as a pin piercing brush roll set A.
- the pin piercing brush roll sets shown in Table 11 were prepared in the same manner.
- the pinning state was confirmed by observation of the initial stage (up to about 100 m from the top), middle stage (50 m before and after 500 m, and end stage (final 100 m) of the film.
- the width of film tearing at pin portion was measured with a scale at about 10 m from the top of the film.
- the brush sets A, B, C afforded good pinning state.
- the brush rolls D, E, F, G showed difficult piercing of the film with the pins and pin tearing frequently occurred. With the lapse of time, bristle material was deformed, worsening the pinning state, and the film was released from the pins.
- the green films (thickness 21 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height from the pin pedestal was 8 mm, the height of the table (a part higher than the pin pedestal) set at the outer side in the width direction of the pin sheet was 2 mm higher than the pin pedestal and 6 mm lower than the pin tip, and the distance between pin sheets was 1140 mm.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- the surface of the table (a part higher than the pin pedestal) set at the outer side in the width direction of the pin sheet was matte-processed by a sandblast treatment, where the surface roughness Ra was 15 ⁇ m.
- the setting of the heat treatment in the tenter was as follows. A two-stage heating (first stage 200° C. for 5 min, temperature was raised at a temperature rise rate of 4° C./sec, second stage 450° C. for 5 min) to allow an imidation reaction to proceed. Thereafter, the film was cooled to room temperature in 5 min, the both ends of the film where flatness was poor were cut off with a slitter, and the film was wound in a roll to give respective brown polyimide films of Examples 76-79.
- the feeding state during heat treatment and the measurement results such as property and the like of the obtained polyimide films are shown in Table 15.
- the obtained film was spread on a surface plate with a clean surface, and an uneven film end producing a space between the film and the surface plate was taken as a flatness failure.
- the both ends of the film were cut until the film end did not rise from the surface of the surface plate and the whole film came into close contact with the surface plate.
- the film width at that time was defined as an effective width.
- the width of film tearing at pin portion was measured with a scale at about 10 m from the top of the film.
- the green films were each obtained in the same manner as in Example 1 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the feeding state during heat treatment and the results such as property and the like of the obtained polyimide films are shown in Table 15.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 40 mm
- the pin height from the pin pedestal was 8 mm.
- the green films (thickness 43 ⁇ m, width 1200 mm) were each obtained in the same manner as in Example 21 from the polyamic acid solutions obtained in Reference Examples 1-4.
- the pins were arranged in such a manner that the distance between the pins would be uniform when the pin sheets were lined up, where the pin height from the pin pedestal was 8 mm, the height of the table (a part higher than the pin pedestal) set at the outer side in the width direction of the pin sheet was 3 mm higher than the pin pedestal and 5 mm lower than the pin tip, and the distance between pin sheets was 1140 mm.
- the length of the pin sheet in the longitudinal direction was 95 mm
- the length in the width direction was 35 mm
- the length in the longitudinal direction of the table set at the outer side in the width direction of the pin sheet was 95 mm
- the length in the width direction was 15 mm
- the periphery of the table was chamfered.
- the surface of the table (a part higher than the pin pedestal) set at the outer side in the width direction of the pin sheet was provided with a groove (width 1 mm, depth 1 mm) in the width direction.
- cavities corresponding to 29% of the whole pin pedestal were formed between pins on the pin pedestal.
- a polymer film particularly a polyimide film
- a tenter type feeding apparatus for drying and a heat treatment deformation of the film in the vicinity of the pin can be suppressed, breakage caused by pores made by piercing the film with pins can be suppressed, the distortion of the whole film can be reduced, and the uneven film thickness can be reduced.
- the obtained film is superior in the quality in the width direction and uniformity in the film thickness.
- the producibility of the polymer film production is also improved. Therefore, it is industrially extremely significant as an apparatus for producing a polymer film or a production method of a polymer film.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Applications Claiming Priority (19)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005129763A JP4821955B2 (ja) | 2005-04-27 | 2005-04-27 | 高分子フィルムの製造装置および高分子フィルムの製造方法 |
| JP2005-129764 | 2005-04-27 | ||
| JP2005-129765 | 2005-04-27 | ||
| JP2005129764A JP4821956B2 (ja) | 2005-04-27 | 2005-04-27 | 高分子フィルムの製造装置および高分子フィルムの製造方法 |
| JP2005129765A JP4843996B2 (ja) | 2005-04-27 | 2005-04-27 | 高分子フィルムの製造装置および高分子フィルムの製造方法 |
| JP2005-129763 | 2005-04-27 | ||
| JP2005173730A JP4821960B2 (ja) | 2005-06-14 | 2005-06-14 | 高分子フィルムの製造装置および高分子フィルムの製造方法 |
| JP2005-173730 | 2005-06-14 | ||
| JP2005208908A JP2007021949A (ja) | 2005-07-19 | 2005-07-19 | 高分子フィルム製造装置および高分子フィルムの製造方法 |
| JP2005-208908 | 2005-07-19 | ||
| JP2005-242834 | 2005-08-24 | ||
| JP2005242834A JP2007055737A (ja) | 2005-08-24 | 2005-08-24 | 高分子フィルムの製造方法および製造装置 |
| JP2005288323A JP5023464B2 (ja) | 2005-09-30 | 2005-09-30 | 高分子フィルムの製造方法および製造装置 |
| JP2005-288322 | 2005-09-30 | ||
| JP2005-288323 | 2005-09-30 | ||
| JP2005288321A JP5023463B2 (ja) | 2005-09-30 | 2005-09-30 | 高分子フィルムの製造方法および製造装置 |
| JP2005288322A JP4835088B2 (ja) | 2005-09-30 | 2005-09-30 | 高分子フィルムの製造方法および製造装置 |
| JP2005-288321 | 2005-09-30 | ||
| PCT/JP2006/308706 WO2006118135A1 (fr) | 2005-04-27 | 2006-04-26 | Dispositif pour produire un film polymerique et procede de production du film polymerique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20090032992A1 US20090032992A1 (en) | 2009-02-05 |
| US8167600B2 true US8167600B2 (en) | 2012-05-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/912,970 Active 2026-11-21 US8167600B2 (en) | 2005-04-27 | 2006-04-26 | Apparatus for producing polymer film and process for producing polymer film |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US8167600B2 (fr) |
| EP (1) | EP1880834A4 (fr) |
| KR (1) | KR20080007388A (fr) |
| WO (1) | WO2006118135A1 (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4967635B2 (ja) * | 2006-12-13 | 2012-07-04 | 東洋紡績株式会社 | 高分子フィルムの製造方法及び高分子フィルムの製造装置 |
| JP2008156090A (ja) * | 2006-12-26 | 2008-07-10 | Toyobo Co Ltd | 高分子フィルムの製造方法及び高分子フィルムの製造装置 |
| JP4964723B2 (ja) * | 2007-09-26 | 2012-07-04 | 富士フイルム株式会社 | ピンテンタ及び溶液製膜方法 |
| US20120040131A1 (en) * | 2010-08-10 | 2012-02-16 | Speer Dwaine D | Composite Panel Having Perforated Foam Core |
| JP2014046656A (ja) * | 2012-09-04 | 2014-03-17 | Du Pont-Toray Co Ltd | ポリイミドフィルムの製造方法 |
| EP2965900A1 (fr) * | 2014-07-09 | 2016-01-13 | Cellpack AG | Procédé et dispositif de fabrication d'ébauche d'emballage, notamment de sac d'emballage |
| KR102013215B1 (ko) * | 2017-10-26 | 2019-08-22 | (주)제일산업 | 메쉬원단의 제직 및 열융착처리 장치 |
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| US2219192A (en) * | 1931-08-10 | 1940-10-22 | Hunter James Machine Co | Tenter drier |
| US2935779A (en) * | 1954-09-03 | 1960-05-10 | Famatex Gmbh | Metal pin rack for fabric stretching machines |
| US3417444A (en) * | 1967-12-20 | 1968-12-24 | Mccreary John | Selvage removing assembly for high speed tenter machines |
| US3597815A (en) * | 1969-08-01 | 1971-08-10 | Bevis Ind Inc | Pin rack for tenter chain link |
| JPS57189819A (en) | 1981-08-01 | 1982-11-22 | Kanegafuchi Chem Ind Co Ltd | Film fixing method in continuous production of synthetic resin film |
| JPS57189821A (en) | 1981-05-18 | 1982-11-22 | Kanegafuchi Chem Ind Co Ltd | Manufacture of synthetic resin film |
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| JPH09230316A (ja) | 1996-02-26 | 1997-09-05 | Teijin Ltd | 光学用フイルムおよびその製造方法 |
| JPH10251420A (ja) | 1998-04-06 | 1998-09-22 | Ube Ind Ltd | 無機微粒子を含有する自己支持性ポリイミドフィルムの製造方法 |
| KR19980068305A (ko) | 1997-02-17 | 1998-10-15 | 한형수 | 등방성 폴리이미드 필름의 제조방법 |
| JPH11254521A (ja) | 1998-03-13 | 1999-09-21 | Teijin Ltd | フィルムの製造方法 |
| JP2000191806A (ja) | 1998-12-24 | 2000-07-11 | Kanegafuchi Chem Ind Co Ltd | ポリイミドフィルムの製造方法及び製造装置 |
| US20030057595A1 (en) | 2001-08-13 | 2003-03-27 | Fuji Photo Film Co., Ltd. | Solvent casting process, polarizing plate protective film, optically functional film and polarizing plate |
| US20030098522A1 (en) * | 2001-10-01 | 2003-05-29 | Toshikazu Nakamura | Solvent casting process and apparatus therefor |
| JP2004136613A (ja) | 2002-10-21 | 2004-05-13 | Konica Minolta Holdings Inc | ポリマーフィルムの製造方法及び位相差フィルム |
-
2006
- 2006-04-26 EP EP06745684A patent/EP1880834A4/fr not_active Withdrawn
- 2006-04-26 US US11/912,970 patent/US8167600B2/en active Active
- 2006-04-26 KR KR1020077027536A patent/KR20080007388A/ko not_active Ceased
- 2006-04-26 WO PCT/JP2006/308706 patent/WO2006118135A1/fr active Application Filing
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| US2219192A (en) * | 1931-08-10 | 1940-10-22 | Hunter James Machine Co | Tenter drier |
| US2935779A (en) * | 1954-09-03 | 1960-05-10 | Famatex Gmbh | Metal pin rack for fabric stretching machines |
| US3417444A (en) * | 1967-12-20 | 1968-12-24 | Mccreary John | Selvage removing assembly for high speed tenter machines |
| US3597815A (en) * | 1969-08-01 | 1971-08-10 | Bevis Ind Inc | Pin rack for tenter chain link |
| JPS57189821A (en) | 1981-05-18 | 1982-11-22 | Kanegafuchi Chem Ind Co Ltd | Manufacture of synthetic resin film |
| JPS57189819A (en) | 1981-08-01 | 1982-11-22 | Kanegafuchi Chem Ind Co Ltd | Film fixing method in continuous production of synthetic resin film |
| US5320267A (en) * | 1989-10-31 | 1994-06-14 | Fuji Photo Film Co., Ltd. | Web transport apparatus |
| JPH0977315A (ja) | 1995-09-14 | 1997-03-25 | Fuji Photo Film Co Ltd | ウエブ又はシートの搬送装置 |
| JPH09230316A (ja) | 1996-02-26 | 1997-09-05 | Teijin Ltd | 光学用フイルムおよびその製造方法 |
| JPH09188763A (ja) | 1997-01-13 | 1997-07-22 | Ube Ind Ltd | ポリイミドフィルム |
| KR19980068305A (ko) | 1997-02-17 | 1998-10-15 | 한형수 | 등방성 폴리이미드 필름의 제조방법 |
| JPH11254521A (ja) | 1998-03-13 | 1999-09-21 | Teijin Ltd | フィルムの製造方法 |
| JPH10251420A (ja) | 1998-04-06 | 1998-09-22 | Ube Ind Ltd | 無機微粒子を含有する自己支持性ポリイミドフィルムの製造方法 |
| JP2000191806A (ja) | 1998-12-24 | 2000-07-11 | Kanegafuchi Chem Ind Co Ltd | ポリイミドフィルムの製造方法及び製造装置 |
| US20030057595A1 (en) | 2001-08-13 | 2003-03-27 | Fuji Photo Film Co., Ltd. | Solvent casting process, polarizing plate protective film, optically functional film and polarizing plate |
| US20030098522A1 (en) * | 2001-10-01 | 2003-05-29 | Toshikazu Nakamura | Solvent casting process and apparatus therefor |
| JP2004136613A (ja) | 2002-10-21 | 2004-05-13 | Konica Minolta Holdings Inc | ポリマーフィルムの製造方法及び位相差フィルム |
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| European Search Report dated Jun. 16, 2010, directed to corresponding International Application No. PCT/JP06/308706; 3 pgs. |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1880834A4 (fr) | 2010-08-04 |
| US20090032992A1 (en) | 2009-02-05 |
| KR20080007388A (ko) | 2008-01-18 |
| WO2006118135A1 (fr) | 2006-11-09 |
| EP1880834A1 (fr) | 2008-01-23 |
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